KR20180034412A - COMPOUND, RESIN, LITHOGRAPHY UNDERWATER FILM FORMING MATERIAL, COMPOSITION FOR FORMING LITHOGRAPHY UNDERWAY FILM, LITHOGRAPHY UNDERLAY FILM AND RESIST PATTERN FORMING METHOD, CIRCUIT PATTERN FORMING METHOD, AND PURIF - Google Patents

Abstract

(식(1) 중, X는, 각각 독립적으로, 산소원자, 황원자 또는 무가교인 것을 나타내고, R¹은, 각각 독립적으로, 할로겐기, 시아노기, 니트로기, 아미노기, 수산기, 티올기, 복소환기, 탄소원자수 1~30의 알킬기, 탄소원자수 2~30의 알케닐기, 탄소원자수 6~40의 아릴기, 및 이들의 조합으로 이루어진 군으로부터 선택되고, 여기서, 이 알킬기, 이 알케닐기 및 이 아릴기는, 에테르 결합, 케톤 결합 또는 에스테르 결합을 포함하고 있을 수도 있고, R²는, 각각 독립적으로, 탄소수 1~30의 알킬기, 탄소수 6~40의 아릴기, 탄소수 2~30의 알케닐기, 티올기 또는 수산기이고, 여기서, R²의 적어도 1개는 수산기 또는 티올기를 포함하는 기이고, m은, 각각 독립적으로, 0~7의 정수이고(여기서, m의 적어도 1개는 1~7의 정수이다.), p는 각각 독립적으로 0 또는 1이고, q는 0~2의 정수이고, n은 1 또는 2이다.)A compound or a resin represented by the following formula (1).

(1), each X independently represents an oxygen atom, a sulfur atom or a non-substituted group; and each R ¹ independently represents a halogen group, a cyano group, a nitro group, an amino group, a hydroxyl group, a thiol group, , An alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, wherein the alkyl group, alkenyl group and aryl group , An ether bond, a ketone bond or an ester bond, and each R ² independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, Wherein at least one of R ² is a group containing a hydroxyl group or a thiol group and m is each independently an integer of 0 to 7 (where at least one of m is an integer of 1 to 7). ), p is independently 0 or 1, q is an integer of 0 to 2, n is 1 or 2.)

Description

COMPOUND, RESIN, LITHOGRAPHY UNDERWATER FILM FORMING MATERIAL, COMPOSITION FOR FORMING LITHOGRAPHY UNDERWAY FILM, LITHOGRAPHY UNDERLAY FILM AND RESIST PATTERN FORMING METHOD, CIRCUIT PATTERN FORMING METHOD, AND PURIF

The present invention relates to a compound or resin having a specific structure. The present invention also provides a lithographic underlayer film forming material containing the above compound and / or resin, a composition for forming a lower layer film for lithography comprising the above material, a lower layer film for lithography obtained from the composition and a method for forming a photoresist pattern using the composition A resist pattern forming method or a circuit pattern forming method). Further, the present invention relates to a method for purifying the above compound or resin.

BACKGROUND ART [0002] In the production of a semiconductor device, fine processing by lithography using a photoresist material is performed. In recent years, with the increasingly high integration and high speed of LSI, further miniaturization by pattern rules is required. In lithography using light exposure, which is currently used as a general-purpose technique, the intrinsic resolution derived from the wavelength of the light source is reaching its limit.

The light source for lithography used for forming a resist pattern is short-wavelengthed by a KrF excimer laser (248 nm) and an ArF excimer laser (193 nm). However, when the resist pattern becomes finer, there arises a problem of resolution or a problem that the resist pattern collapses after development, so that it is required to reduce the thickness of the resist. However, when the thinning of the resist is simply performed, it becomes difficult to obtain a film thickness of a resist pattern sufficient for substrate processing. Accordingly, there has been a need for a process for manufacturing a resist underlayer film between a resist and a semiconductor substrate to be processed, as well as a resist pattern, so that the resist underlayer film has a function as a mask at the time of substrate processing.

At present, various kinds of resist undercoat films for such processes are known. For example, unlike a conventional resist underlayer film having a high etching rate, a resist underlayer film having a selectivity ratio of a dry etching rate close to that of a resist is realized. When a predetermined energy is applied, a terminal group is eliminated and a sulfonic acid residue (See, for example, Japanese Unexamined Patent Publication (Kokai) No. 2004-177668) discloses a material for forming a lower layer film for a multi-layer resist process containing a resin component having at least a substituent which generates a hydroxyl group and a solvent. In addition, a resist underlayer film material containing a polymer having a specific repeating unit has been proposed to realize a resist underlayer film having a selectivity to a dry etching rate lower than that of a resist (see Patent Document 2 (Japanese Patent Application Laid- 271838). Further, a resist underlayer film having a selection ratio of a dry etching rate smaller than that of a semiconductor substrate is realized, and includes a polymer obtained by copolymerizing a repeating unit of acenaphthylene and a repeating unit having a substituted or unsubstituted hydroxy group (See Patent Document 3 (Japanese Patent Laid-Open Publication No. 2005-250434)).

On the other hand, an amorphous carbon underlayer film formed by CVD using a methane gas, an ethane gas, an acetylene gas, or the like as a raw material is well known as a material having a high etching resistance in such a resist underlayer film. However, from the viewpoint of processes, a resist underlayer film material capable of forming a resist underlayer film by a wet process such as spin coating or screen printing is required.

In addition, the present inventors have found that a naphthalene formaldehyde polymer containing a specific constituent unit and a lithographic underlayer film containing an organic solvent, which are excellent in optical characteristics and etching resistance and can be applied to a solvent and can be subjected to a wet process, (Patent Document 4: WO2009 / 072465 and Patent Document 5: WO2011 / 034062).

On the other hand, as for the method of forming the intermediate layer used in the formation of the resist lower layer film in the three-layer process, for example, a method of forming a silicon nitride film (see Patent Document 6 (Japanese Patent Laid-Open Publication No. 2002-334869) , And a CVD forming method of a silicon nitride film (see Patent Document 7 (WO2004 / 066377)). As an intermediate layer material for a three-layer process, a material containing a silsesquioxane-based silicon compound is known (see Patent Document 8 (Japanese Unexamined Patent Application Publication No. 2007-226170) and Patent Document 9 (Japanese Patent Application Laid- -226204).

Japanese Patent Application Laid-Open No. 2004-177668 Japanese Patent Application Laid-Open No. 2004-271838 Japanese Patent Application Laid-Open No. 2005-250434 International Publication No. 2009/072465 International Publication No. 2011/034062 Japanese Patent Application Laid-Open No. 2002-334869 International Publication No. 2004/066377 Japanese Patent Application Laid-Open No. 2007-226170 Japanese Patent Application Laid-Open No. 2007-226204

As described above, a number of conventionally known lower layer film forming materials for lithography have been proposed. However, in addition to having high solubility in solvents capable of applying a wet process such as spin coating and screen printing, and high etching resistance No, there is a demand for the development of new materials.

In addition, in recent years, with the progress of miniaturization of a pattern, even a substrate having a step (in particular, a minute space or a hole pattern) has a step filling property which makes it possible to uniformly fill even the corners of the step, Mars is required. Particularly, a resist layer (resist underlayer) disposed on the substrate side is highly required.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems, and its object is to provide a compound or a resin, which can apply a wet process and is useful for forming a photoresist underlayer film excellent in etching resistance, and a lithographic underlayer A forming material, a composition for forming a lower layer film for lithography comprising the above material, a lower layer film for lithography obtained from the composition, and a method for forming a photoresist pattern using the composition (a method for forming a resist pattern or a method for forming a circuit pattern) . It is still another object of the present invention to provide a purification method useful for the purification of the compound and the resin.

DISCLOSURE OF THE INVENTION The inventors of the present invention have made intensive investigations to solve the above problems, and as a result, they have found that the aforementioned problems can be solved by using a compound or a resin having a specific structure, and the present invention has been completed. That is, the present invention is as follows.

[1] A compound represented by the following formula (1).

[Chemical Formula 1]

(1), each X independently represents an oxygen atom, a sulfur atom or a non-substituted group; and each R ¹ independently represents a halogen group, a cyano group, a nitro group, an amino group, a hydroxyl group, a thiol group, , An alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, wherein the alkyl group, alkenyl group and aryl group , An ether bond, a ketone bond or an ester bond, and each R ² independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, Wherein at least one of R ² is a group containing a hydroxyl group or a thiol group and m is each independently an integer of 0 to 7 (where at least one of m is an integer of 1 to 7). ), p is independently 0 or 1, q is an integer of 0 to 2, n is 1 or 2.)

[2] The compound according to [1], wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).

(2)

(In the formula (1-1), R ¹ , R ² , m, p, q and n are as defined in the formula (1).)

[3] The compound according to [2], wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-2).

(3)

(2), each R ³ is independently an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, and R ¹ , p, q, , M ² is independently an integer of 0 to 5, m ³ is independently an integer of 1 to 6, m ² + m ³ is an integer of 1 to 6 It is an integer.)

[4] The compound according to [3], wherein the compound represented by the formula (1-2) is a compound represented by the following formula (1-3).

[Chemical Formula 4]

(In the formula (1-3), R ¹ , R ³ , p, q and n are the same as those described in the formula (1), and m ² is the same as that described in the formula (1-2).)

[5] The compound according to [4], wherein the compound represented by the formula (1-3) is a compound represented by the following formula (1-4).

[Chemical Formula 5]

(In the formula (1-4), R ¹ and q are as defined in the formula (1).)

[6] The compound according to [5], wherein the compound represented by the formula (1-4) is a compound represented by the following formula (IMX-1).

[Chemical Formula 6]

[7] A resin obtained by using the compound according to any one of [1] to [6] as a monomer.

[8] The resin according to the above-mentioned [7], which is obtained by reacting the compound described in any one of [1] to [6] with a compound having a crosslinking reactivity.

[9] The method according to the above [8], wherein the crosslinkable compound is at least one compound selected from aldehyde, ketone, carboxylic acid, carboxylic acid halide, halogen containing compound, amino compound, imino compound, isocyanate and unsaturated hydrocarbon group- Lt; / RTI >

[10] A resin having a structure represented by the following formula (2).

(7)

(In the formula (2), each X independently represents an oxygen atom, a sulfur atom or a non-substituted group, and each R ¹ independently represents a halogen group, a cyano group, a nitro group, an amino group, a hydroxyl group, , An alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, wherein the alkyl group, alkenyl group and aryl group , An ether bond, a ketone bond or an ester bond, and each R ² independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, Y is a single bond or an alkylene group having 1 to 20 carbon atoms, m is, independently of each other, an integer of 0 to 6 (provided that at least one of R ² is a group containing a hydroxyl group or a thiol group) Here, at least one of m is an integer of 1 to 6), p is Independently 0 or 1, q is an integer from 0 to 2, and n is 1 or 2.)

[11] A lower layer film forming material for lithography, comprising the compound according to any one of [1] to [6] and / or the resin according to any one of the above [7] to [10].

[12] A composition for forming a lower layer film for lithography, comprising the underlayer film forming material for lithography and the solvent according to [11] above.

[13] The composition for forming a lower layer film for lithography as described in [12], further comprising an acid generator.

[14] The composition for forming a lower layer film for lithography as described in [12] or [13], further comprising a crosslinking agent.

[15] A lithographic underlayer film formed using the composition for forming a lower layer film for lithography according to any one of [12] to [14].

[16] A method for manufacturing a semiconductor device, comprising the steps of: forming a lower layer film on a substrate using the lower layer film forming composition according to any one of the above [12] to [14]; and forming at least one photoresist layer on the lower layer film Irradiating a predetermined region of the photoresist layer with radiation, and developing the resist pattern.

[17] A method of forming a lower layer film on a substrate by using the composition for forming a lower layer according to any one of [12] to [14], and forming a resist interlayer film material containing silicon atoms on the lower layer film Forming a photoresist layer on at least one of the intermediate layer films, irradiating a predetermined region of the photoresist layer with radiation, developing the photoresist layer to form a resist pattern, Forming a circuit pattern on the substrate by etching the intermediate layer film using the resist pattern as a mask, etching the lower layer film using the obtained interlayer film pattern as an etching mask, and etching the substrate using the obtained lower layer film pattern as an etching mask Way.

[18] A method for producing a resin composition, comprising: preparing a solution containing a compound according to any one of [1] to [6] or a resin according to any one of [7] A method for purifying a compound or a resin, comprising the step of extracting an acidic aqueous solution by contacting.

Wherein the acidic aqueous solution is one or more inorganic acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or an aqueous solution of at least one inorganic acid selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, The purification method according to the above-mentioned [18], wherein the aqueous solution is an aqueous solution of at least one organic acid selected from the group consisting of p-toluenesulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid.

[20] The method according to any one of [1] to [20], wherein the organic solvent which is not optionally miscible with water is at least one selected from the group consisting of toluene, 2-heptanone, cyclohexanone, cyclopentanone, methylisobutylketone, propylene glycol monomethyl ether acetate, Butyl, or ethyl acetate, as described in [18] or [19] above.

[21] The purification method according to any one of [18] to [20] above, further comprising a step of bringing the solution and an acidic aqueous solution into contact with each other to conduct an extraction treatment and further subjecting the aqueous solution to extraction treatment.

According to the present invention, there is provided a compound or resin and a lithographic underlayer film forming material containing the same, which can be applied to a wet process and is useful for forming a photoresist underlayer film excellent in etching resistance, a lithographic underlayer film forming A lower layer film for lithography obtained from the composition, and a photoresist pattern forming method (a resist pattern forming method or a circuit pattern forming method) using the composition. Further, according to the present invention, it is possible to provide a purification method useful for the purification of the compound and the resin.

Hereinafter, embodiments of the present invention will be described. The following embodiments are illustrative of the present invention, and the present invention is not limited to the embodiments.

The present invention relates to a compound or a resin useful for forming a photoresist underlayer film (hereinafter simply referred to as " underlayer film ") capable of applying a wet process and having excellent etching resistance, and a lithography A film for forming a lower layer film, and a composition for forming a lower layer film for lithography including the above material can be realized. The compound or resin of the present invention and the lower layer film forming material for lithography comprising the same are excellent in solvent solubility. Furthermore, since the composition for forming a lower layer film for lithography and the composition for forming a lower layer film for lithography of the present invention use a compound or resin having a specific structure, the composition is also excellent in curability. As a result, deterioration of the film at the time of high-temperature baking is suppressed, and the underlayer film excellent in etching resistance against plasma etching of the fluorine gas can be formed. Further, since the adhesion with the resist layer is also excellent, an excellent resist pattern can be formed.

[compound]

The compound of this embodiment is represented by the following formula (1).

[Chemical Formula 8]

In the above formula (1), each X independently represents an oxygen atom, a sulfur atom or a non-substituted group.

R ¹ each independently represents a halogen atom, a cyano group, a nitro group, an amino group, a hydroxyl group, a thiol group, a heterocyclic group, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, Aryl groups, and combinations thereof. Here, the alkyl group, the alkenyl group and the aryl group may include an ether bond, a ketone bond or an ester bond.

R ² each independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a thiol group or a hydroxyl group. Provided that at least one of R < ² > is a group containing a hydroxyl group or a thiol group.

The alkyl group and the alkenyl group described above may be any of linear, branched or cyclic.

m each independently represents an integer of 0 to 7; Provided that at least one of m is an integer of 1 to 7; p is independently 0 or 1, q is an integer of 0 to 2, and n is 1 or 2. On the other hand, when p represents 0, a portion represented by a naphthalene structure (bicyclic structure) in the formula (1) becomes a phenyl structure (i.e., a monocyclic structure).

The compound represented by the formula (1) has a relatively low molecular weight and its structure is rigid and has high heat resistance, so that it can be used even under a high-temperature baking condition. Further, even in the case of a substrate having a step (particularly, a minute space or a hole pattern) at a relatively low molecular weight and low viscosity point, it is easy to uniformly fill the corner of the step difference. As a result, The forming material may have relatively favorable embedding characteristics. High etching resistance is also imparted.

The molecular weight of the compound of this embodiment (the above-mentioned "compound represented by the above formula (1)") is preferably 300 to 3000, more preferably 300 to 2000, further preferably 300 to 1000 desirable. On the other hand, the molecular weight can be measured by the method described in the following Examples.

The compound represented by the formula (1) is a group in which at least one of R ² contains a hydroxyl group or a thiol group from the viewpoints of easiness of curing and solubility in an organic solvent.

The compound represented by the formula (1) is more preferably a compound represented by the following formula (1-1) from the viewpoint of the feedability of the starting material.

[Chemical Formula 9]

In the formula (1-1), R ¹ , R ² , m, p, q and n are the same as those described in the formula (1).

The compound represented by the above formula (1-1) is more preferably a compound represented by the following formula (1-2) from the viewpoint of solubility in an organic solvent.

[Chemical formula 10]

Wherein R ¹ , p, q and n are the same as those described in the above formula (1), R ³ is independently an alkyl group having 1 to 30 carbon atoms, an alkyl group having 6 to 40 carbon atoms An aryl group and an alkenyl group having 2 to 30 carbon atoms, m ² is independently an integer of 0 to 5, m ³ is independently an integer of 1 to 6, and m ² + m ³ is an integer of 1 to 6 It is an integer. The alkyl group and the alkenyl group may be any of linear, branched or cyclic.

The compound represented by the formula (1-2) is particularly preferably a compound represented by the following formula (1-3) from the viewpoint of solubility in a further organic solvent.

(11)

In the formula (1-3), R ¹ , R ³ , p, q and n are the same as those described in the formula (1), and m ² is the same as that described in the formula (1-2).

From the viewpoint of good fluidity, the compound represented by the formula (1-3) is a compound represented by the formula (1-3) in which n = 1, that is, represented by the following formula (1-4) Is preferable.

[Chemical Formula 12]

In the formula (1-4), R ¹ and q are as defined in the formula (1).

Further, the compound represented by the above formula (1-4) is particularly preferably a compound represented by the following formula (IMX-1) from the viewpoints of ease of production and availability of raw materials.

[Chemical Formula 13]

Specific examples of the compound represented by the formula (1) are illustrated below, but the compounds are not limited thereto.

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

In the specific examples of the compound represented by the formula (1) described above, R ¹ , R ² , q and m are as defined in the formula (1).

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

In the specific examples of the compound represented by the formula (1) described above, R ¹ , R ² , q and m are as defined in the formula (1).

The compound represented by the formula (1) used in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis method thereof is not particularly limited. For example, the compound represented by the formula (1) can be obtained by subjecting a phenol, thiophenol, naphthol or thiophenol and a corresponding aldehyde to polycondensation reaction under an atmospheric pressure under an acid catalyst. Further, if necessary, the above-described synthesis may be carried out under pressure.

Examples of the phenol include phenol, methylphenol, methoxybenzene, catechol, hydroquinone, trimethylhydroquinone, and the like, but are not limited thereto. These may be used singly or in combination of two or more. Among them, it is more preferable to use hydroquinone or trimethylhydroquinone as the above-mentioned phenol because it can easily form a xanthene structure.

The thiophenols include, for example, benzenethiol, methylbenzenethiol, methoxybenzenethiol, benzenedithiol, trimethylbenzenedithiol, and the like, but they are not particularly limited thereto. These may be used singly or in combination of two or more. Of these, use of benzenedithiol or trimethylbenzenedithiol as the thiophenols is more advantageous in that the structure of the thioxanthene can be easily produced.

The naphthols include, for example, naphthol, methylnaphthol, methoxynaphthol, naphthalene diol, and the like, but are not limited thereto. These may be used singly or in combination of two or more. Of these, naphthalene diols are more preferable as the naphthols because they can easily form a benzoxaphthene structure.

Examples of the thiophenols include naphthalene thiol, methylnaphthalene thiol, methoxynaphthalene thiol, and naphthalene dithiol. However, the present invention is not limited thereto. These may be used singly or in combination of two or more. Among them, naphthalene dithiol is more advantageous than the thiophenols in that thiobenzo xanthene structure can be easily produced.

Examples of the aldehydes include 4-formylimidazole, 1-methyl-4-formylimidazole, 2-methyl-4-formylimidazole, Imidazole, 5-formylimidazole, 1-methyl-5-formylimidazole, 2-methyl-5-formylimidazole, 2- Methylimidazole, formylimidazole, 4,5-diformylimidazole, 2-methyl-4,5-diformylimidazole, and the like, but they are not particularly limited thereto. These may be used singly or in combination of two or more.

Among these aldehydes, 4-formylimidazole and 1-methyl-4-formylimidazole are preferably used because they give high solubility and high etching resistance, and 4-formyl It is more preferable to use midazol.

The acid catalyst that can be used in the synthesis reaction of the compound represented by the formula (1) can be appropriately selected from known ones and is not particularly limited. As such an acid catalyst, inorganic acids and organic acids are widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid and hydrofluoric acid, and organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, , Organic acids such as maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid and naphthalenedisulfonic acid , Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride, and solid acids such as silicotungstic acid, tungstic acid, silicomolybdic acid or phosphomolybdic acid, and the like. Of these, from the viewpoint of production, organic acids and solid acids are preferable, and p-toluenesulfonic acid or sulfuric acid is preferably used from the viewpoint of production easiness, ease of handling, and the like.

On the other hand, the acid catalyst may be used alone or in combination of two or more. The amount of the acid catalyst to be used is not particularly limited, but it is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material, depending on the type of raw material to be used and the type of catalyst to be used and further reaction conditions.

In the reaction, a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction between the aldehyde to be used and the phenol, thiophenol, naphthol, or thionaphthol proceeds, and can be appropriately selected from known ones. For example, water , Methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or a mixed solvent thereof. On the other hand, one solvent may be used alone, or two or more solvents may be used in combination. The amount of these solvents to be used can be suitably set according to the kind of the starting material to be used and the type of catalyst used and furthermore the reaction conditions and is not particularly limited but it is preferably 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material Do. Further, the reaction temperature in the above-mentioned reaction can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 ° C.

In order to obtain the compound represented by the formula (1) of the present embodiment, the reaction temperature is preferably high, and specifically preferably in the range of 60 to 200 ° C. The reaction can be carried out by appropriately selecting a known method, and is not particularly limited. However, it is also possible to use a method in which phenols, thiophenols, naphthols or thiophenols, aldehydes or catalysts are added in a batch, or phenols, thiophenols , Naphthol, or thionaphthol or aldehyde in the presence of a catalyst.

After completion of the polycondensation reaction, isolation of the obtained compound can be carried out according to the conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials and catalysts present in the system, by employing a general method such as raising the temperature of the reaction pot to 130 to 230 ° C and removing volatile components to about 1 to 50 mmHg, Compound can be obtained.

Preferable reaction conditions include using 1 mol to an excess amount of phenols, thiophenols, naphthols or thiophenols per mole of aldehydes and 0.001 to 1 mol of an acid catalyst and at 20 to 20 Minute to about 100 hours.

After completion of the reaction, the desired product can be isolated by a known method. For example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, the reaction product is cooled to room temperature, filtered and separated, and the resulting solid is filtered, dried and then purified by column chromatography Separation and purification, solvent removal, filtration and drying are carried out to obtain the target compound represented by the above formula (1).

[Suzy]

The resin of this embodiment is a resin obtained by using the compound represented by the above formula (1) as a monomer. In other words, the resin of the present embodiment is a resin having a unit structure derived from the general formula (1). As a specific example of the resin, a resin having a structure represented by the following formula (2) can be given.

(23)

In the formula (2), X represents, independently of each other, an oxygen atom, a sulfur atom or a non-substituted group.

R ¹ each independently represents a halogen atom, a cyano group, a nitro group, an amino group, a hydroxyl group, a thiol group, a heterocyclic group, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, Aryl groups, and combinations thereof. Here, the alkyl group, the alkenyl group and the aryl group may include an ether bond, a ketone bond or an ester bond.

R ² each independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a thiol group or a hydroxyl group. Provided that at least one of R < ² > is a group containing a hydroxyl group or a thiol group.

The alkyl and alkenyl groups described above may be any of linear, branched or cyclic.

Y is a single bond or an alkylene group having 1 to 20 carbon atoms, m is independently an integer of 0 to 6, p is independently 0 or 1, q is an integer of 0 to 2, n is 1 Or 2. The alkenyl group may be linear, branched or cyclic, and is preferably a linear or branched alkylene group.

In the resin having the structure represented by the formula (2) in the present embodiment, the compound represented by the above formula (1) may be referred to as a crosslinkable compound (hereinafter also referred to as " crosslinkable reactive monomer " ). ≪ / RTI >

As the monomer having a crosslinking reactivity, known ones can be used without particular limitation, so long as they can react with the compound represented by the formula (1) to be oligomerized or polymerized. Specific examples of the crosslinkable monomer include a compound selected from the group consisting of aldehyde, ketone, carboxylic acid, carboxylic acid halide, halogen-containing compound, amino compound, imino compound, isocyanate, unsaturated hydrocarbon group- And the like, but are not particularly limited to these.

Specific examples of the resin having a structure represented by the formula (2) include a resin obtained by condensation reaction of a compound represented by the formula (1) with an aldehyde, which is a monomer having a crosslinking reactivity, .

Examples of the aldehyde used in the novolak of the compound represented by the formula (1) include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde Benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, hydroxymethylbenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, But are not limited to these. Of these, formaldehyde is more preferable. On the other hand, these aldehydes may be used singly or in combination of two or more. The amount of the aldehyde to be used is not particularly limited, but is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles, per 1 mole of the compound represented by the formula (1).

In the condensation reaction of the compound represented by the formula (1) with the aldehyde, a reaction solvent may be used. The reaction solvent in the polycondensation is not particularly limited and may be selected from known ones, and examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, Mixed solvents and the like. On the other hand, one solvent may be used alone, or two or more solvents may be used in combination.

The amount of these solvents to be used can be suitably set according to the kind of the starting material to be used and the type of catalyst used and furthermore the reaction conditions and is not particularly limited but it is preferably 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material Do. The reaction temperature may be appropriately selected depending on the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 占 폚. The reaction can be carried out by appropriately selecting a known method and is not particularly limited. However, the method of introducing the compound represented by the formula (1), the aldehyde and the catalyst in a batch, And then dropping the compound or aldehyde to be displayed in the presence of a catalyst.

After completion of the polycondensation reaction, isolation of the obtained compound can be carried out according to the conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials and catalysts present in the system, by employing a general method such as raising the temperature of the reaction pot to 130 to 230 ° C and removing volatile components to about 1 to 50 mmHg, A novolak resin can be obtained.

Here, the resin of the present embodiment may be a homopolymer of the compound represented by the formula (1), or may be a copolymer with other phenols. Examples of the copolymerizable phenol include phenol, cresol, dimethyl phenol, trimethyl phenol, butyl phenol, phenyl phenol, diphenyl phenol, naphthyl phenol, resorcinol, methyl resorcinol, catechol, , Methoxyphenol, methoxyphenol, propylphenol, pyrogallol, thymol and the like, but they are not particularly limited to these.

In addition to the above-mentioned other phenols, the resin of the present embodiment may be one which is copolymerized with a polymerizable monomer. Examples of such copolymerizable monomers include monomers such as naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, Dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, vinyl norbornene, pinene, limonene, and the like, but they are not particularly limited thereto. On the other hand, the resin of the present embodiment may be a copolymer of two or more atoms (for example, a two to four member system) of the compound represented by the formula (1) and the above-described phenol, (2 to 4 member system) copolymer of the compound and the above-described copolymerizable monomer, or a copolymer of the compound represented by the formula (1) and the above-mentioned phenol and the above-mentioned copolymerizable monomer (For example, a 3 to 4 member system) copolymer.

On the other hand, the molecular weight of the resin of the present embodiment is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene is preferably 500 to 20,000, and more preferably 750 to 10,000. From the viewpoint of increasing the crosslinking efficiency and suppressing the volatile components in the baking, the resin of the present embodiment preferably has a dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) within a range of 1.1 to 7, And preferably 1.1 to 2. [ On the other hand, the Mn can be obtained by the method described in the following Examples.

From the viewpoint that the compound represented by the above-described formula (1) and / or the resin obtained by using the above compound as a monomer can be more easily applied to a wet process, it is preferable that the resin has a high solubility in a solvent. More specifically, when these solvents and / or resins are solvents in which 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) are used as the solvent, % Or more. Here, the solubility in PGME and / or PGMEA is defined as " mass of resin / (mass of resin + mass of solvent) x 100 (mass%) ". For example, 10 g of the resin represented by the formula (1) and / or the resin obtained by using the above compound as a monomer is evaluated as "dissolved" in 90 g of the PGMEA can be obtained by reacting the compound represented by the formula (1) and / The solubility of the resin obtained by using the above compound as a monomer in PGMEA is " 10% by mass or more ", and the case where the solubility is " less than 10% by mass "

[Lower layer film forming material for lithography]

The lower layer film forming material for lithography of the present embodiment contains at least one kind of material selected from the group consisting of a compound represented by the above-described formula (1) and a resin obtained by using the above compound as a monomer. In the present embodiment, the material is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and more preferably 50 to 100% by mass in the material for forming a lithographic underlayer from the viewpoints of coating properties and quality stability %, And particularly preferably 100% by mass. On the other hand, the material for forming a lower layer film for lithography of the present embodiment may contain a known material for forming a lower layer film for lithography in the range where the effect of the present invention is not impaired.

[Composition for forming a lower layer film for lithography]

The composition for forming a lower layer film for lithography of the present embodiment may contain, in addition to the above-described compound represented by the formula (1) and / or a resin obtained by using the above compound as a monomer, a solvent, a crosslinking agent, It may contain other ingredients. These optional components are described below.

[menstruum]

The composition for forming a lower layer film for lithography of the present embodiment may contain a solvent. As the solvent, those known in the art can be suitably used as long as the compound represented by the above-mentioned formula (1) and / or the resin obtained by using the above compound as a monomer are dissolved at least.

Specific examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; Ester solvents such as ethyl acetate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate and methyl hydroxyisobutyrate; Alcohol solvents such as methanol, ethanol, isopropanol and 1-ethoxy-2-propanol; Aromatic hydrocarbons such as toluene, xylene, and anisole, and the like, but are not particularly limited to these. These solvents may be used singly or in combination of two or more.

Of these solvents, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate and anisole are particularly preferable from the viewpoint of safety.

The content of the solvent is not particularly limited, but is preferably 100 to 10,000 parts by mass, more preferably 200 to 5,000 parts by mass, and most preferably 200 to 1,000 parts by mass with respect to 100 parts by mass of the lower layer film forming material from the viewpoints of solubility and film- Mass part is more preferable.

[Crosslinking agent]

The composition for forming a lower layer film for lithography according to the present embodiment may contain a crosslinking agent if necessary from the viewpoint of suppressing intermixing and the like. Specific examples of the crosslinking agent that can be used in the present embodiment include a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, an epoxy compound, a thioepoxy compound, an isocyanate compound, an azide compound, As the substituent (crosslinkable group), at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is exemplified, but not limited thereto. On the other hand, these crosslinking agents may be used singly or in combination of two or more. They may also be used as additives. On the other hand, it is also possible to introduce the crosslinkable group as a pendant group into the polymer side chain of the compound represented by the formula (1) and / or the resin obtained by using the above compound as a monomer. Further, a compound containing a hydroxy group can also be used as a crosslinking agent.

Specific examples of the melamine compound include, for example, compounds obtained by methoxymethylating 1 to 6 methylol groups of hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, or mixtures thereof, hexamethoxyethyl melamine, Hexaacyloxymethyl melamine, compounds obtained by acyloxymethylating 1 to 6 methylol groups of hexamethylol melamine, or mixtures thereof, and the like. Specific examples of the epoxy compound include, for example, tris (2,3-epoxypropyl) isocyanurate, trimethylol methane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylol ethane triglycidyl ether And the like.

Specific examples of the guanamine compound include, for example, a compound obtained by methoxymethylating 1 to 4 methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, tetramethylolguanamine, or a mixture thereof, A compound obtained by acyloxymethylating 1 to 4 methylol groups of tetraethyloxyguanamine, tetramethylolguanamine, or a mixture thereof, and the like. Concrete examples of the glycoluril compound include, for example, 1 to 4 methoxymethylated compounds of methylol groups of tetramethylolglycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril and tetramethylolglycoluril Or a mixture thereof, a compound obtained by acyloxymethylating 1 to 4 methylol groups of tetramethylolglycoluril, or a mixture thereof. Specific examples of the urea compound include, for example, a compound obtained by methoxymethylating 1 to 4 methylol groups of tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea, or a mixture thereof, tetramethoxyethylurea, etc. .

Specific examples of the compound containing an alkenyl ether group include, for example, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetra Methylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol Tetravinyl ether, sorbitol pentabinyl ether, trimethylolpropane trivinyl ether, and the like.

In the composition for forming a lower layer film for lithography of the present embodiment, the content of the crosslinking agent is not particularly limited, but it is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass relative to 100 parts by mass of the lithographic underlayer film forming material, To 40 parts by mass. In the above-mentioned preferred range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, the antireflection effect increases, and the film formability after crosslinking tends to increase.

[Acid generator]

The composition for forming a lower layer film for lithography of the present embodiment may contain an acid generator if necessary, from the viewpoint of further promoting a crosslinking reaction by heat or the like. As the acid generator, it is known that an acid is generated by pyrolysis and an acid is generated by light irradiation, and any of them can be used.

As the acid generator,

1) an onium salt of the following formula (P1a-1), (P1a-2), (P1a-3)

2) a diazomethane derivative of the formula (P2)

3) a glyoxime derivative represented by the following formula (P3)

4) bis-sulfone derivatives of the formula (P4)

5) sulfonic acid esters of N-hydroxyimide compounds of formula (P5)

6)? -Ketosulfonic acid derivatives,

7) disulfone derivatives,

8) Nitrobenzylsulfonate derivatives,

9) Sulfonic acid ester derivatives

And the like, but are not particularly limited to these. On the other hand, these acid generators may be used singly or in combination of two or more.

≪ EMI ID =

^Wherein R ^101a , R ^101b and R ^101c are each independently a straight, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms; An aryl group having 6 to 20 carbon atoms; Or an aralkyl group or an aryloxoalkyl group having 7 to 12 carbon atoms, and some or all of hydrogen atoms of these groups may be substituted with an alkoxy group or the like. Further, R ^101b and R ^101c may form a ring, and when forming a ring, R ^101b and R ^101c each independently represent an alkylene group having 1 to 6 carbon atoms. K ^- represents an unconjugated counter ion. R ^101d , R ^101e , R ^101f and R ^101g each independently represent a hydrogen atom added to R ^101a , R ^101b and R ^101c . When R ^101d , R ^101e , R ^101d , R ^101e and R ^101f may form a ring, R ^101d , R ^101e and R ^101d, and R ^101e and R ^101f may form a ring. Or represents a heteroaromatic ring having a nitrogen atom in the ring in the formula.

R ^101a , R ^101b , R ^101c , R ^101d , R ^101e , R ^101f , and R ^101g described above may be the same or different from each other. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, A cyclohexyl group, a cycloheptyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, an adamantyl group, and the like can be given. Examples of the alkenyl group include, but are not limited to, a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include, but are not limited to, a 2-oxocyclopentyl group and a 2-oxocyclohexyl group, and a 2-oxopropyl group, a 2-cyclopentyl- Hexyl-2-oxoethyl group, and 2- (4-methylcyclohexyl) -2-oxoethyl group. Examples of the oxoalkenyl group include, but are not limited to, a 2-oxo-4-cyclohexenyl group and a 2-oxo-4-propenyl group. Examples of the aryl group include, but are not limited to, a phenyl group and a naphthyl group, and p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p- , and m-tert-butoxyphenyl group; An alkylphenyl group such as a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group or a dimethylphenyl group; Alkylnaphthyl groups such as methylnaphthyl and ethylnaphthyl; Alkoxynaphthyl groups such as methoxynaphthyl group and ethoxynaphthyl group; Dialkylnaphthyl groups such as dimethylnaphthyl and diethylnaphthyl; And a dialkoxynaphthyl group such as a methoxynaphthyl group and a diethoxynaphthyl group. Examples of the aralkyl group include, but are not limited to, a benzyl group, a phenylethyl group, and a phenethyl group. Examples of the aryloxoalkyl group include, but are not limited to, 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) And 2-aryl-2-oxoethyl group such as oxoethyl group. Examples of the non-nucleophilic counter ion of K ^- include, but are not limited to, halide ions such as chloride ion and bromide ion; Fluoroalkylsulfonates such as triflate, 1,1,1-trifluoroethanesulfonate and nonafluorobutanesulfonate; Aryl sulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; And alkyl sulfonates such as mesylate and butane sulfonate.

In the case where R ^101d , R ^101e , R ^101f and R ^101g are a heteroaromatic ring having a nitrogen atom in the ring, the heteroaromatic ring may be an imidazole derivative (for example, imidazole, 4-methylimidazole , 4-methyl-2-phenylimidazole and the like), pyrazole derivatives, furazan derivatives, pyrroline derivatives (for example, pyrroline and 2-methyl-1-pyrroline), pyrrolidine derivatives Pyrrolidine, pyrrolidine, N-methylpyrrolidone), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (for example, pyridine, methylpyridine, ethylpyridine, Butylpyridine, 4-tert-butylpyridine, benzyl (3-methylphenyl) pyridine, butylpyridine, 4- Pyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl- Pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, pyrimidine derivatives, pyrimidine derivatives, (Such as quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinolin derivatives, quinoline derivatives, A phenanthrene derivative, a phenanthrene derivative, a 1,10-phenanthroline derivative, an adenine derivative, an adenosine derivative, a guanine derivative, a pyrimidine derivative, a pyrimidine derivative, Derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

The onium salts of the formulas (P1a-1) and (P1a-2) have a function as a photoacid generator and a thermal acid generator. The onium salt of the above formula (P1a-3) has a function as a thermal acid generator.

(25)

In the formula (P1b), R ^102a and R ^102b each independently represent a straight, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ represents a straight, branched or cyclic alkylene group of 1 to 10 carbon atoms. R ^104a and R ^104b each independently represent a 2-oxoalkyl group having 3 to 7 carbon atoms. K ^- represents an unconjugated counter ion.

Specific examples of R ^102a and R ^102b include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, An octyl group, a cyclopentyl group, a cyclohexyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, and a cyclohexylmethyl group. Specific examples of R ¹⁰³ include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, , 1,2-cyclohexylene group, 1,3-cyclopentylene group, 1,4-cyclooctylene group and 1,4-cyclohexanedimethylene group. Specific examples of R ^104a and R ^104b include, but are not limited to, a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is the same as described in formulas (P1a-1), (P1a-2) and (P1a-3).

(26)

In the formula (P2), R ¹⁰⁵ and R ¹⁰⁶ each independently represents a linear, branched or cyclic alkyl or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, 12 < / RTI >

Examples of the alkyl group represented by R ¹⁰⁵ and R ¹⁰⁶ include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, An acyl group, an acyl group, a heptyl group, an octyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group and an adamantyl group. Examples of the halogenated alkyl group include, but are not limited to, trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-trichloroethyl group, nonafluorobutyl group, etc. have. The aryl group includes, but is not limited to, a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p- An alkoxyphenyl group such as a butoxyphenyl group; Alkylphenyl groups such as a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group and a dimethylphenyl group. Examples of the halogenated aryl group include, but are not limited to, a fluorophenyl group, a chlorophenyl group, and a 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include, but are not limited to, a benzyl group, a phenethyl group, and the like.

(27)

In formula (P3), R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are each independently a straight, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms; An aryl group or a halogenated aryl group having 6 to 20 carbon atoms; Or an aralkyl group having 7 to 12 carbon atoms. R ¹⁰⁸ and R ¹⁰⁹ may combine with each other to form a cyclic structure. When a cyclic structure is formed, R ¹⁰⁸ and R ¹⁰⁹ each represent a straight or branched alkylene group having 1 to 6 carbon atoms.

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group represented by R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ include the same groups as described for R ¹⁰⁵ and R ¹⁰⁶ . On the other hand, examples of the alkylene groups represented by R ¹⁰⁸ and R ¹⁰⁹ include, but are not limited to, a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

(28)

In the formula (P4), ^R101a and ^R101b are the same as described above.

[Chemical Formula 29]

In the formula (P5), R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms. Some or all of the hydrogen atoms of these groups may be further substituted with a linear or branched alkyl or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group, or a phenyl group. R ¹¹¹ represents a linear, branched or substituted alkyl, alkenyl or alkoxyalkyl group having 1 to 8 carbon atoms, a phenyl group, or a naphthyl group. Some or all of the hydrogen atoms in these groups may be further substituted with an alkyl or alkoxy group having 1 to 4 carbon atoms; A phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group or an acetyl group; A heteroaromatic group having 3 to 5 carbon atoms; Or a chlorine atom or a fluorine atom.

Here, the arylene group of R ¹¹⁰ is not limited to the following, but for example, 1,2-phenylene group, 1,8-naphthylene group and the like can be given. Examples of the alkylene group include, but are not limited to, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a phenylethylene group, and a norbornane-2,3-diyl group. Examples of the alkenylene group include, but are not limited to, 1,2-vinylene group, 1-phenyl-1,2-vinylene group and 5-norbornene-2,3-diyl group. As the R ¹¹¹ is an alkyl group, those similar to the R ^101a R ~ ^101c. Examples of the alkenyl group include, but are not limited to, vinyl, 1-propenyl, allyl, 1-butenyl, Hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl group and the like have. Examples of the alkoxyalkyl group include, but are not limited to, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl , Propoxyethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, A methoxypentyl group, an ethoxypentyl group, a methoxyhexyl group, and a methoxyheptyl group.

Examples of the alkyl group having 1 to 4 carbon atoms which may be further substituted include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, Butyl group and the like. Examples of the alkoxy group having 1 to 4 carbon atoms include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, . Examples of the phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group, or an acetyl group include, but are not limited to, phenyl, tolyl, p-tert-butoxyphenyl, Phenyl group, p-nitrophenyl group and the like. Examples of the heteroaromatic group having 3 to 5 carbon atoms include, but are not limited to, a pyridyl group and a furyl group.

Specific examples of acid generators include, but are not limited to, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, triethylammonium nonafluorobutanesulfonate, nonafluorobutanesulfones Triethylammonium camphorsulfonate, tetraphenylammonium tetrafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, tetramethylammonium p-toluenesulfonate, tetrafluoroethylene tetrafluoroborate, tetrafluoroethylene tetrafluoroborate, (P-tert-butoxyphenyl) phenyl iodonium, p-toluenesulfonic acid diphenyl iodonium, p-toluenesulfonic acid (p-tert- (P-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid bis (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, -Butoxyphenyl) phenylsulfonium, trifluoromethane P-toluenesulfonic acid bis (p-tert-butoxyphenyl) sulfonium chloride, p-toluenesulfonic acid bis (p- p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, tri Trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl p-toluenesulfonate (2-oxocyclo Hexyl) sulfonium trifluoromethanesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trifluoro Trinaphthylsulfonium methanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxo (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethylene bis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate] Onium salts such as 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate; Bis (cyclopentylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis Di (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis Bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (Amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert- butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl- diazomethane derivatives such as (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane; Bis- (p-toluenesulfonyl) -? - dimethylglyoxime, bis- (p-toluenesulfonyl) -? - diphenylglyoxime, bis- (p- toluenesulfonyl) -? - dicyclohexylglyoxime (P-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis- (p- toluenesulfonyl) -2,3-pentanedione glyoxime, bis- Bis (n-butanesulfonyl) -? - dicyclohexylglyoxime, bis- (n-butanesulfonyl) -α-diphenylglyoxime, bis Bis (n-butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis- (methanesulfonyl) -? - dimethylglyoxime, Bis (trifluoromethanesulfonyl) -? - dimethylglyoxime, bis- (1,1,1-trifluoroethanesulfonyl) -? - dimethylglyoxime, bis- (tert- (perfluorooctanesulfonyl) -? - dimethylglyoxime, bis- (cyclohexanesulfonyl) -? - dimethylglyoxime, bis- (benzenesulfonyl) -? - dimethylglyoxime, (P-tert-butylbenzenesulfonyl) -? - dimethylglyoxime, bis- (xylenesulfonyl) -? - dimethylglyoxime, bis glyoxime derivatives such as? -dimethylglyoxime and bis- (camphorsulfonyl) -? - dimethylglyoxime; Bis-naphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, bis Bis-sulfone derivatives such as benzenesulfonylmethane; ? -Ketosulfone derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane; Diphenylsulfone derivatives such as diphenyldisulfone derivatives and dicyclohexyldisulfone derivatives, nitrobenzylsulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate ; Benzene such as 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p- toluenesulfonyloxy) Sulfonic acid ester derivatives; N-hydroxysuccinimide ethanesulfonic acid ester, N-hydroxysuccinimide methane sulfonic acid ester, N-hydroxysuccinimide trifluoromethane sulfonic acid ester, N-hydroxysuccinimide ethane sulfonic acid ester, Hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinic ester Imide p-toluenesulfonic acid ester, N-hydroxysuccinimide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester, N-hydroxysuccinimide benzenesulfonic acid Esters, N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimide Acid esters, N-hydroxymaleimide methanesulfonic acid esters, N-hydroxymaleimide ethanesulfonic acid esters, N-hydroxy-2-phenylmaleimide methanesulfonic acid esters, N-hydroxyglutarimide methanesulfonic acid Ester, N-hydroxyglutarimide benzenesulfonic acid ester, N-hydroxyphthalimide methanesulfonic acid ester, N-hydroxyphthalimide benzenesulfonic acid ester, N-hydroxyphthalimide trifluoromethanesulphonate N-hydroxynaphthalimide benzenesulfonic acid ester, N-hydroxy-5-aminobenzenesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, N- Norbornene-2,3-dicarboxyimide methanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboxyimide trifluoromethanesulfonic acid ester, N-hydroxy- 2,3-dicarboxyimide p-toluene And sulfonic acid ester derivatives of N-hydroxyimide compounds such as sulfonic acid esters.

Among them, in particular, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-tert- (P-tert-butoxyphenyl) sulfone, p-toluenesulfonic acid triphenylsulfonium p-toluenesulfonate, p- Trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) Hexyl) sulfonium, and 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate; Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis Bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis Diazomethane derivatives such as dimethan; Glyoxime derivatives such as bis- (p-toluenesulfonyl) -? - dimethylglyoxime and bis (n-butanesulfonyl) -? - dimethylglyoxime; bissulfone derivatives such as bisnaptylsulfonylmethane; N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2- Propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxy Sulfonic acid ester derivatives of N-hydroxyimide compounds such as naphthalimide benzenesulfonic acid ester and the like are preferably used.

In the composition for forming a lower layer film for lithography of the present embodiment, the content of the acid generator is not particularly limited, but is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the lithographic underlayer film forming material, Is 0.5 to 40 parts by mass. With the above-described preferable range, the amount of acid generated is increased, the crosslinking reaction tends to increase, and the occurrence of the mixing phenomenon with the resist layer tends to be suppressed.

[Basic compound]

Furthermore, the composition for forming a lower layer film for lithography of the present embodiment may contain a basic compound from the viewpoint of improving storage stability and the like.

The basic compound plays a role of an acid to prevent a slight amount of acid generated from an acid generator from proceeding a crosslinking reaction. Examples of such basic compounds include nitrogen-containing compounds having primary, secondary or tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, carboxy groups, nitrogen-containing compounds having a sulfonyl group, A nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like.

Specific examples of the first class aliphatic amines include, but are not limited to, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec- Butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylene Diamine, tetraethylenepentamine, and the like. Specific examples of the secondary aliphatic amines include, but are not limited to, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di N, N-dimethylaniline, dicyclohexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, and the like. Specific examples of the tertiary aliphatic amines include, but are not limited to, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri tri-n-butylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridecylamine, tricetylamine, tricetylamine, N N, N ', N'-tetramethyltetraethylenepentamine, N, N', N'-tetramethylmethylenediamine, N, .

Specific examples of the mixed amines include, but are not limited to, dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, and the like. Specific examples of aromatic amines and heterocyclic amines include, but are not limited to, aniline derivatives (for example, aniline, N-methylaniline, N-ethyl aniline, N-propylaniline, N, Dianthraquinone, 2,4-dinitroaniline, 2,6-diethylaniline, 2,4-dinitroaniline, 2,4-dinitroaniline, 2,6-di (P-tolyl) amine, methyl diphenyl amine, triphenyl amine, phenylenediamine, naphthylamine, diaminonaphthalene, Pyrrole derivatives such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole and N-methylpyrrole, oxazole derivatives such as oxazole, Sol, etc.), thiazole derivatives (for example, thiazole, isothiazole, etc.), imidazole derivatives (for example imidazole, 4-methylimidazole, 2-methyl-1-pyrroline), pyrrolidine derivatives (for example, pyrrolidine, pyrrolidine, pyrrolidine, Imidazolidine derivatives, pyridine derivatives (for example, pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, N-methylpyrrolidine, N-methylpyrrolidine, , 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, 4-methylpyridine, 4-methylpyridine, 4- , Butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine Etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives An isoindoline derivative, a 1H-indazole derivative, an indoline derivative, a quinoline derivative (e.g., quinoline, 3-quinolinecarbonitrile and the like), an isoquinoline derivative, a cinnoline derivative, Quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenantholidine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives , Adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, and uridine derivatives.

Further, specific examples of the nitrogen-containing compound having a carboxyl group include, but are not limited to, amino benzoic acid, indole carboxylic acid, amino acid derivatives (e.g., nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, Leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine). Specific examples of the nitrogen-containing compound having a sulfonyl group include, but are not limited to, 3-pyridine sulfonic acid, p-toluenesulfonic acid pyridinium, and the like. Specific examples of the nitrogen-containing nitrogen compound having a hydroxyl group, the nitrogen-containing nitrogen compound having a hydroxyphenyl group, and the alcoholic nitrogen compound include, but are not limited to, 2-hydroxypyridine, aminocresol, 2,4- 2-aminoethanol, 3-aminoethanol, 3-aminoethanol, 3-aminoethanol, 2-aminoethanol, 2-aminoethanol, Amino-1-propanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- 1- (2-hydroxyethoxy) ethyl] piperazine, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- Dienone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3- -2-pyrrole Dean ethanol, and 1-aziridine ethanol, N- (2- hydroxyethyl) phthalimide, N- (2- hydroxyethyl) iso nicotinamide. Specific examples of the amide derivative include, but are not limited to, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, , Benzamide, and the like. Specific examples of the imide derivative include, but are not limited to, phthalimide, succinimide, maleimide and the like.

In the composition for forming a lower layer film for lithography of the present embodiment, the content of the basic compound is not particularly limited, but is preferably 0.001 to 2 parts by mass relative to 100 parts by mass of the lithographic underlayer film forming material, 0.01 to 1 part by mass. By setting the above-mentioned range, there is a tendency that the storage stability is enhanced without excessively damaging the crosslinking reaction.

In addition, the composition for forming a lower layer film for lithography of the present embodiment may contain other resins and / or compounds for the purpose of imparting thermosetting property and controlling absorbance. Examples of other resins and / or compounds include naphthol resins, xylene resin naphthol-modified resins, phenol-modified resins of naphthalene resins, polyhydroxystyrene, dicyclopentadiene resins, (meth) acrylates, dimethacrylates, Naphthalene rings such as methacrylate, tetramethacrylate, vinylnaphthalene and polyacenaphthylene, biphenyl rings such as phenanthrenequinone and fluorene, and heterocyclic rings having hetero atoms such as thiophene and indene. A resin not containing an aromatic ring; A resin or a compound containing an alicyclic structure such as a rosin resin, a cyclodextrin, an adamantane (poly) ol, a tricyclodecane (poly) ol or a derivative thereof, and the like. Furthermore, the composition for forming a lower layer film for lithography of the present embodiment may contain known additives. The known additives include, but are not limited to, ultraviolet absorbers, surfactants, colorants, and nonionic surfactants.

[Lower layer film for lithography and method of forming multi-layer resist pattern]

The lower layer film for lithography of the present embodiment is formed by using the composition for forming a lower layer film for lithography of the present embodiment.

(A-1) forming a lower layer film by using the composition for forming a lower layer film for lithography of the present embodiment on a substrate, and a step (A-2) forming a photoresist layer on the photoresist layer; and (A-3) a step of irradiating a predetermined region of the photoresist layer with radiation after the second formation process to perform development.

Further, another pattern forming method of the present embodiment includes a step (B-1) of forming a lower layer film by using the composition for forming a lower layer film for lithography of the present embodiment on a substrate, a step (B-3) forming at least one photoresist layer on the intermediate layer film; and a step (B-3) of forming at least one photoresist layer on the intermediate layer film. A step (B-4) of irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern after the step (B-3); and a step (B-5) forming the pattern on the substrate by etching the interlayer film, etching the lower layer film using the obtained interlayer film pattern as an etching mask, and etching the substrate using the obtained lower layer film pattern as an etching mask.

The forming method of the lower layer film for lithography of the present embodiment is not particularly limited as long as it is formed from the composition for forming a lower layer film for lithography of the present embodiment, and a known method can be applied. For example, after the composition for forming a lower layer for lithography of the present embodiment is applied on a substrate by a known coating method such as a spin coating method or a screen printing method, or the like, and then the organic solvent is volatilized or removed, .

At the time of forming the lower layer film, it is preferable to perform baking in order to suppress the occurrence of the mixing phenomenon with the upper layer resist and accelerate the crosslinking reaction. In this case, the bake temperature is not particularly limited, but is preferably in the range of 80 to 450 占 폚, more preferably 200 to 400 占 폚. The baking time is not particularly limited, but is preferably within a range of 10 seconds to 300 seconds. On the other hand, the thickness of the lower layer film can be suitably selected in accordance with the required performance, and is not particularly limited, but is usually preferably about 30 nm to 20,000 nm, more preferably 50 nm to 15,000 nm.

In the case of a two-layer process, a silicon-containing resist layer or a single-layer resist made of ordinary hydrocarbon, a silicon-containing intermediate layer on a three-layer process, and a silicon- It is preferable to produce a layer. In this case, known photoresist materials for forming the resist layer can be used.

When a lower layer film is formed on a substrate, in the case of a two-layer process, a silicon-containing resist layer or a single-layer resist made of a common hydrocarbon can be formed on the lower layer film. In the case of a three-layer process, a silicon-containing intermediate layer on the lower layer film and a single-layer resist layer containing no silicon on the silicon-containing intermediate layer can be produced. In these cases, the photoresist material for forming the resist layer can be appropriately selected from known ones and is not particularly limited.

As a silicon-containing resist material for a two-layer process, a silicon-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative is used as a base polymer from the viewpoint of oxygen gas etching resistance, , And if necessary, a positive type photoresist material containing a basic compound or the like is preferably used. As the silicon atom-containing polymer, known polymers used in this type of resist material can be used.

As the silicon-containing intermediate layer for the three-layer process, an intermediate layer of a polysilsesquioxane base is preferably used. Reflection layer on the intermediate layer, there is a tendency that the reflection can be effectively suppressed. For example, in a process for 193 nm exposure, when a material containing a large amount of aromatic groups as a lower layer film and having high substrate etching resistance is used, the k value tends to be high and substrate reflection tends to be high. By suppressing reflection to the intermediate layer, To 0.5% or less. The intermediate layer having such an antireflection effect is not particularly limited, but polysilsesquioxane which is crosslinked with acid or heat, in which a light absorber having a phenyl group or a silicon-silicon bond is introduced for 193 nm exposure is preferably used.

An intermediate layer formed by a chemical vapor deposition (CVD) method may also be used. The intermediate layer which is highly effective as an antireflection film produced by the CVD method is not limited to the following, but for example, a SiON film is known. In general, formation of an intermediate layer by a wet process such as spin coating or screen printing is simpler and more cost-effective than CVD. On the other hand, the upper-layer resist in the three-layer process may be either positive or negative, and may be the same as a commonly used single-layer resist.

Furthermore, the lower layer film of the present embodiment can be used as a general antireflection film for a single-layer resist or as a foundation material for suppressing pattern collapse. Since the lower layer film of the present embodiment is excellent in etching resistance for undercut processing, a function as a hard mask for undercut processing can also be expected.

In the case of forming the resist layer by the photoresist material, a wet process such as spin coating or screen printing is preferably used as in the case of forming the lower layer film. After the resist material is applied by spin coating or the like, prebaking is usually carried out. It is preferable that the prebaking is performed at 80 to 180 DEG C for 10 to 300 seconds. Thereafter, a resist pattern is obtained by performing exposure in accordance with a conventional method, and performing post exposure bake (PEB) and development. On the other hand, the thickness of the resist film is not particularly limited, but is generally from 30 nm to 500 nm, more preferably from 50 nm to 400 nm.

The exposure light may be suitably selected in accordance with the photoresist material to be used. Generally, high energy rays having a wavelength of 300 nm or less, specifically, excimer lasers of 248 nm, 193 nm and 157 nm, soft X-rays of 3 nm to 20 nm, electron beams, X-rays and the like can be given.

The resist pattern formed by the above-described method has pattern collapse suppressed by the lower layer film of the present embodiment. Thus, by using the lower layer film of the present embodiment, a finer pattern can be obtained, and the amount of exposure necessary for obtaining the resist pattern can be lowered.

Next, etching is performed using the obtained resist pattern as a mask. As the etching of the lower layer film in the two-layer process, gas etching is preferably used. As gas etching, etching using oxygen gas is favorable. It is also possible to add an inert gas such as He or Ar or CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO _{2 or} H ₂ gas in addition to the oxygen gas. Further, gas etching can be performed using only CO, CO ₂ , NH ₃ , N ₂ , NO _{2, and} H ₂ gas without using oxygen gas. Particularly, the latter gas is preferably used for side wall protection for preventing undercut of the pattern side wall.

On the other hand, also in the etching of the intermediate layer in the three-layer process, gas etching is preferably used. As the gas etching, the same materials as described in the two-layer process described above can be applied. Particularly, it is preferable that the processing of the intermediate layer in the three-layer process is carried out using a resist pattern as a mask using a fluorine-based gas. Thereafter, the lower layer film can be processed by performing, for example, oxygen gas etching using the intermediate layer pattern as a mask as described above.

Here, when an inorganic hard mask intermediate layer film is formed as an intermediate layer, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) are formed by a CVD method, an ALD method, or the like. The method of forming the nitride film is not limited to the following example, but may be, for example, a method disclosed in Japanese Unexamined Patent Publication No. 2002-334869 (Patent Document 6 described above), International Publication No. 2004/066377 (Patent Document 7 described above) Method can be used. A photoresist film can be formed directly on the intermediate layer film. An organic antireflection film (BARC) may be formed on the intermediate layer film by spin coating and a photoresist film may be formed thereon.

As the intermediate layer, an intermediate layer of a polysilsesquioxane base is also preferably used. By making the resist interlayer film serve as an antireflection film, there is a tendency to effectively suppress reflection. Specific examples of the material of the intermediate layer of the polysilsesquioxane base are not limited to the following examples. For example, Japanese Unexamined Patent Application Publication No. 2007-226170 (Patent Document 8), Japanese Patent Application Publication No. 2007-226204 Patent Document 9) can be used.

For example, when the substrate is SiO ₂ or SiN, the etching is mainly performed using a flon-based gas. In the case of p-Si or Al, when W is a chlorine-based or bromine-based gas, Etching can be performed. When the substrate is etched with a fluorine-based gas, the silicon-containing resist of the two-layer resist process and the silicon-containing intermediate layer of the three-layer process are peeled off simultaneously with the substrate processing. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer is separately peeled off. In general, dry etch-off is performed with a chlorine-based gas after processing the substrate.

The lower layer film of the present embodiment is characterized by excellent etching resistance of these substrates. Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, and the like can be given as the substrate, although known substrates can be appropriately selected and used. Further, the substrate may be a laminate having a workpiece (substrate to be processed) on a substrate (support). Various low-k films such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu and Al- And usually a material different from that of the substrate (support) is used. On the other hand, the thickness of the substrate or the workpiece to be processed is not particularly limited, but is usually about 50 nm to 10,000 nm, more preferably 75 nm to 5,000 nm.

[Method for purifying compound or resin]

The method for purifying a compound or a resin of the present embodiment is a method for preparing a solution (A) by dissolving a resin represented by the formula (1) or a resin obtained by using the compound as a monomer in an organic solvent which is not optionally miscible with water, (A) is brought into contact with an acidic aqueous solution. According to the extraction process, after the metal compound contained in the compound (A) containing the compound or the resin and the organic solvent is transferred to the aqueous phase, the organic phase and the aqueous phase are separated and purified. By the purification method of the present embodiment, the content of various metal components in the resin obtained by using the compound represented by the formula (1) or the above compound as a monomer can be remarkably reduced.

The " organic solvent that is not miscible with water " used in the present embodiment is not particularly limited, but an organic solvent that can be safely applied to a semiconductor manufacturing process is preferable. The amount of the organic solvent to be used is usually about 1 to 100 times by mass with respect to the total amount of the compound represented by the formula (1) or the resin obtained using the compound as a monomer.

Specific examples of the organic solvent used in the purification method include ethers such as diethyl ether and diisopropyl ether, esters such as ethyl acetate, n-butyl acetate and isobutyl acetate, methyl ethyl ketone, Ketones such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (manufactured by Nippon Polyurethane Industry Co., Ltd.), ethylene glycol monobutyl ether acetate Propylene glycol monoethyl ether acetate), aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and chloroform, and the like, . Of these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methylisobutylketone, propylene glycol monomethyl ether acetate and ethyl acetate are preferable, and cyclohexanone, propylene glycol monomethyl ether acetate, , 2-diethoxy ketone, butyl acetate, or ethyl acetate is preferable. These organic solvents may be used alone or in combination of two or more.

The acidic aqueous solution used in the present embodiment is appropriately selected from an aqueous solution in which generally known organic or inorganic compounds are dissolved in water. For example, an aqueous solution of an inorganic acid in which an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid is dissolved in water, or an aqueous solution of an inorganic acid such as acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, Sulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid and the like in water. These acidic aqueous solutions may be used alone or in combination of two or more. Among these acidic aqueous solutions, aqueous solutions of sulfuric acid, nitric acid, and carboxylic acids such as acetic acid, oxalic acid, tartaric acid and citric acid are preferable, and furthermore, aqueous solutions of sulfuric acid, oxalic acid, tartaric acid and citric acid are preferable. It is believed that the polyvalent carboxylic acid such as oxalic acid, tartaric acid, and citric acid is coordinated to the metal ion and a chelating effect is generated, so that the metal can be removed more. In addition, the water used herein is preferably one having a small metal content, for example, ion-exchanged water, etc., in accordance with the object of the present invention.

The pH of the acidic aqueous solution used in the present embodiment is not particularly limited, but if the acidity of the aqueous solution becomes too large, it may not adversely affect the resin represented by the formula (1) or the resin obtained by using the compound as a monomer. Usually, the pH range is about 0 to 5, and more preferably about 0 to 3.

The amount of the acidic aqueous solution to be used in this embodiment is not particularly limited, but if the amount is too small, it is necessary to increase the number of times of extraction for metal removal. On the other hand, if the amount of aqueous solution is too large, May cause problems with the image quality. The amount of the aqueous solution to be used is usually from 10 to 200% by mass, and preferably from 20 to 100% by mass, based on the solution of the resin represented by the formula (1) dissolved in an organic solvent or the resin obtained using the above compound as a monomer.

In this embodiment, a solution (A) containing an acidic aqueous solution as described above, a resin obtained by using the compound represented by the formula (1) or a compound obtained by using the compound as a monomer and an organic solvent which is not optionally miscible with water, .

The temperature at which extraction treatment is carried out is usually 20 to 90 占 폚, preferably 30 to 80 占 폚. The extraction operation is carried out, for example, by mixing by stirring or the like, and then left to stand. As a result, the metal component contained in the solution containing the compound represented by the formula (1) or the resin obtained by using the compound as a monomer and the organic solvent shifts to the aqueous phase. Further, by this operation, the acidity of the solution is lowered, and deterioration of the resin obtained by using the compound represented by the formula (1) or the above compound as a monomer can be suppressed.

The obtained mixture is separated into a solution phase containing a resin represented by the formula (1) or a resin obtained by using the above compound as a monomer and an organic solvent, and a water phase, whereby the compound represented by the formula (1) A solution containing a resin obtained as a monomer and an organic solvent is recovered. The time for which the solution is allowed to stand is not particularly limited. However, if the time for standing still is too short, separation between the aqueous phase containing the organic solvent and the aqueous phase will be deteriorated, which is not preferable. Normally, the standing time is at least 1 minute, more preferably at least 10 minutes, and even more preferably at least 30 minutes. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, setting, and separation a plurality of times.

In the case where such an extraction treatment is carried out using an acidic aqueous solution, after the treatment, the solution is extracted from the aqueous solution, and a solution containing a resin represented by the formula (1) or a resin obtained by using the compound as a monomer and an organic solvent (A) is preferably subjected to extraction treatment with water again. The extraction operation is carried out by mixing well by stirring or the like, and then standing. The obtained solution is separated into a solution phase containing a resin represented by the formula (1) or a resin obtained by using the above compound as a monomer and an organic solvent, and a water phase, so that the compound represented by the formula (1) As a monomer, and a solution phase containing an organic solvent are recovered. In addition, the water used herein is preferably one having a small metal content, for example, ion-exchanged water, etc., in accordance with the object of the present invention. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, setting, and separation a plurality of times. The conditions such as the ratio of use in the extraction treatment, the temperature and the time are not particularly limited, but may be the same as in the case of the above-mentioned contact treatment with the acidic aqueous solution.

The water mixed in the solution containing the resin represented by the formula (1) thus obtained or the resin obtained by using the compound as the monomer and the organic solvent can be easily removed by an operation such as distillation under reduced pressure. If necessary, an organic solvent may be added to adjust the concentration of the resin obtained by using the compound represented by the formula (1) or the above compound as a monomer to an arbitrary concentration.

A method of obtaining only a resin obtained by using a compound represented by the formula (1) or a solution obtained by using the above compound as a monomer and a solution containing an organic solvent as a monomer or a compound represented by the formula (1) Removal by re-precipitation, separation by re-precipitation, and combinations thereof. If necessary, known processes such as a concentration operation, a filtration operation, a centrifugation operation, and a drying operation can be performed.

Example

Hereinafter, the present invention will be described in detail with reference to Synthesis Examples and Examples. However, the present invention is not limited to these examples at all.

(Carbon concentration and oxygen concentration)

The carbon concentration and oxygen concentration (mass%) were measured by organic element analysis using the following apparatus.

Apparatus: CHN coder MT-6 (manufactured by Yanako Analytical Industry Co., Ltd.)

(Molecular Weight)

Was measured by LC-MS analysis using Acquity UPLC / MALDI-Synapt HDMS manufactured by Water.

(Molecular weight in terms of polystyrene)

The weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene were determined by gel permeation chromatography (GPC) analysis and the degree of dispersion (Mw / Mn) was determined.

Device: Shodex GPC-101 (manufactured by Showa Denko K.K.)

Column: KF-80M x 3

Eluent: THF 1 ml / min

Temperature: 40 ° C

(Solubility)

The solubility of the compound in 1-methoxy-2-propanol (PGME) and propylene glycol monomethyl ether acetate (PGMEA) was measured at 23 占 폚, and the results were evaluated according to the following criteria.

Evaluation A: 10% by mass or more

Evaluation B: 5 mass% or more and less than 10 mass%

Evaluation C: Less than 5% by mass

(Synthesis Example 1) Synthesis of IMX-1

An internal 300 mL container equipped with a stirrer, a cooling tube and a burette was prepared. To this vessel, 7.68 g (80 mmol) of 4-formylimidazole (manufactured by Shikoku Chemicals), 25.6 g (160 mmol) of 2,7-dihydroxynaphthalene (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) And 100 mL of oxalic acid (manufactured by Kanto Chemical Co., Ltd.) was added thereto. Further, 7.6 g (40 mmol) of p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Ltd.) was added thereto to prepare a reaction solution. The reaction solution was stirred at 90 캜 for 6 hours to carry out the reaction. Next, neutralization treatment was performed with a 48% aqueous solution of sodium hydroxide (reagent manufactured by Kanto Chemical Co.), and the reaction solution was concentrated. Subsequently, 80 mL of n-heptane (reagent manufactured by Kanto Chemical Co.) was added to precipitate the reaction product, cooled to room temperature, filtered, and separated. The solids obtained by filtration were dried. Thereafter, separation and purification were carried out by column chromatography to obtain 13.2 g of the desired compound (IMX-1) represented by the following formula.

On the other hand, the following peaks were found by 400 MHz- ¹ H-NMR and it was confirmed that the following chemical structure was obtained.

≪ ¹ > H-NMR: (d-DMSO, internal standard TMS)

(ppm) 9.4 (2H, O-H), 6.8-7.7 (12H, Ph-H)

(30)

As a result of the organic element analysis, the obtained compound (IMX-1) had a carbon concentration of 75.8% and an oxygen concentration of 12.7%.

The molecular weight of the resulting compound was measured by the above-mentioned method and found to be 380.

As a result of evaluating the solubility in PGME and PGMEA, the compound (IMX-1) was evaluated to have excellent solubility at 10 mass% or more (evaluation A). As a result, the compound (IMX-1) was evaluated to be sufficiently applicable to an edge bead rinse solution (PGME / PGMEA mixture solution) having high storage stability in a solution state and widely used in a semiconductor micro- .

(Synthesis Example 2) Synthesis of IMX-2

An internal 300 mL container equipped with a stirrer, a cooling tube and a burette was prepared. To the vessel were added 7.68 g (80 mmol) of 4-formylimidazole (manufactured by Shikoku Chemicals), 25.6 g (160 mmol) of 2,6-dihydroxynaphthalene (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) And 100 mL of oxalic acid (manufactured by Kanto Chemical Co., Ltd.) was added thereto. Further, 7.6 g (40 mmol) of p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Ltd.) was added thereto to prepare a reaction solution. The reaction solution was stirred at 90 캜 for 6 hours to carry out the reaction. Next, neutralization treatment was performed with a 48% aqueous solution of sodium hydroxide (reagent manufactured by Kanto Chemical Co.), and the reaction solution was concentrated. Subsequently, 100 mL of n-heptane (reagent manufactured by Kanto Chemical Co.) was added to precipitate the reaction product, cooled to room temperature, and filtered to separate. The solids obtained by filtration were dried. Separation and purification were then carried out by column chromatography to obtain 9.2 g of the desired compound (IMX-2) represented by the following formula.

On the other hand, the following peaks were found by 400 MHz- ¹ H-NMR and it was confirmed that the following chemical structure was obtained.

≪ ¹ > H-NMR: (d-DMSO, internal standard TMS)

(ppm) 9.3 (2H, O-H), 6.8-7.7 (12H, Ph-H)

(31)

As a result of the organic element analysis, the obtained compound (IMX-2) had a carbon concentration of 75.8% and an oxygen concentration of 12.7%.

The molecular weight of the resulting compound was measured by the above-mentioned method and found to be 380.

As a result of evaluating the solubility in PGME and PGMEA, the compound (IMX-2) was evaluated to have excellent solubility at 10 mass% or more (evaluation A). Accordingly, the compound (IMX-2) was evaluated to be sufficiently applicable to an edge bead rinsing liquid (PGME / PGMEA mixture solution) having high storage stability in a solution state and widely used in a semiconductor microfabrication process.

(Synthesis Example 3) Synthesis of IMX-3

An internal 300 mL container equipped with a stirrer, a cooling tube and a burette was prepared. To this vessel was added 7.68 g (80 mmol) of 4-formylimidazole (manufactured by Shikoku Chemicals), 29.8 g (160 mmol) of 4,4-biphenol (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), γ-butyrolactone Chemical reagent) was added. Further, 7.6 g (40 mmol) of p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Ltd.) was added thereto to prepare a reaction solution. The reaction solution was stirred at 100 캜 for 4 hours to carry out the reaction. Next, neutralization treatment was performed with a 48% aqueous solution of sodium hydroxide (reagent manufactured by Kanto Chemical Co.), and then 200 mL of distilled water was added to precipitate a reaction product. After cooling to room temperature, filtration was performed to separate. The solids obtained by filtration were dried. Thereafter, separation and purification were carried out by column chromatography to obtain 6.3 g of the desired compound (IMX-3) represented by the following formula.

On the other hand, the following peaks were found by 400 MHz- ¹ H-NMR and it was confirmed that the following chemical structure was obtained.

≪ ¹ > H-NMR: (d-DMSO, internal standard TMS)

(ppm) 9.1 (4H, O-H), 6.5-7.7 (16H, Ph-H)

(32)

As a result of the organic element analysis, the obtained compound (IMX-3) had a carbon concentration of 74.6% and an oxygen concentration of 14.2%.

The molecular weight of the obtained compound was measured by the above-mentioned method and found to be 450.

As a result of evaluating the solubility in PGME and PGMEA, the compound (IMX-3) was evaluated to have excellent solubility at 10 mass% or more (evaluation A). Thus, it was evaluated that the compound (IMX-3) was sufficiently applicable to the edge bead rinsing liquid (PGME / PGMEA mixture solution), which has high storage stability in the solution state and is widely used in the semiconductor microfabrication process.

(Synthesis Example 4) Synthesis of IMX-4

An internal 300 mL container equipped with a stirrer, a cooling tube and a burette was prepared. (80 mmol) of 2-phenylimidazole-4-carboxyaldehyde (manufactured by Shikoku Chemicals), 25.6 g (160 mmol) of 2,6-dihydroxynaphthalene (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) -Butyrolactone (reagent manufactured by Kanto Chemical Co., Ltd.) was added thereto. Further, 7.6 g (40 mmol) of p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Ltd.) was added thereto to prepare a reaction solution. The reaction solution was stirred at 90 캜 for 4 hours to carry out the reaction. Next, neutralization treatment was performed with a 48% aqueous solution of sodium hydroxide (reagent manufactured by Kanto Chemical Co.), and then 200 mL of distilled water was added to precipitate a reaction product. After cooling to room temperature, filtration was performed to separate. The solids obtained by filtration were dried. Thereafter, separation and purification were carried out by column chromatography to obtain 9.1 g of the desired compound (IMX-4) represented by the following formula.

On the other hand, the following peaks were found by 400 MHz- ¹ H-NMR and it was confirmed that the following chemical structure was obtained.

≪ ¹ > H-NMR: (d-DMSO, internal standard TMS)

(ppm) 9.3 (2H, O-H), 6.5-8.2 (16H, Ph-H)

(33)

As a result of the organic element analysis, the obtained compound (IMX-4) had a carbon concentration of 78.9% and an oxygen concentration of 10.5%.

The molecular weight of the compound thus obtained was measured by the above-mentioned method and found to be 456.

As a result of evaluating the solubility in PGME and PGMEA, the compound (IMX-4) had a stability that can be stored in a solution state at an amount of 5 mass% or more (evaluation B), and an edge bead rinse liquid PGME / PGMEA mixed solution).

(Synthesis Example 5) Synthesis of IMX-5

An internal 300 mL container equipped with a stirrer, a cooling tube and a burette was prepared. (80 mmol) of 2-butyl-4-chloroimidazole-5-carboxyaldehyde (manufactured by Shikoku Chemicals) and 25.6 g (160 mmol) of 2,6-dihydroxynaphthalene (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) And 100 mL of? -Butyrolactone (reagent manufactured by Kanto Chemical Co., Ltd.). Further, 7.6 g (40 mmol) of p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Ltd.) was added thereto to prepare a reaction solution. The reaction solution was stirred at 90 캜 for 4 hours to carry out the reaction. Next, neutralization treatment was performed with a 48% aqueous solution of sodium hydroxide (reagent manufactured by Kanto Chemical Co.), and then 200 mL of distilled water was added to precipitate a reaction product. After cooling to room temperature, filtration was performed to separate. The solids obtained by filtration were dried. Thereafter, separation and purification were carried out by column chromatography to obtain 10.3 g of the desired compound (IMX-5) represented by the following formula.

On the other hand, the following peaks were found by 400 MHz- ¹ H-NMR and it was confirmed that the following chemical structure was obtained.

≪ ¹ > H-NMR: (d-DMSO, internal standard TMS)

(ppm) 9.3 (2H, O-H), 6.5-7.5 (10H, Ph-H)

(34)

As a result of the organic element analysis, the obtained compound (IMX-5) had a carbon concentration of 71.4% and an oxygen concentration of 10.1%.

With respect to the obtained compound, the molecular weight was measured by the above-mentioned method and found to be 470.

As a result of evaluating the solubility in PGME and PGMEA, the compound (IMX-5) was evaluated to have excellent solubility at 10 mass% or more (evaluation A). Accordingly, it was evaluated that the compound (IMX-5) had a high storage stability in a solution state and was sufficiently applicable to an edge bead rinse solution (PGME / PGMEA mixture solution) widely used in a semiconductor microfabrication process.

(Synthesis Example 6) Synthesis of Resin (IMR-1)

A four liter flask with an internal volume of 1 L, equipped with a Dimros cooling tube, a thermometer and a stirrer, was prepared. 26.0 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of IMX-1 obtained in Synthesis Example 1, 21.0 g of a 40 mass% formalin aqueous solution (280 mmol as formaldehyde, manufactured by Mitsubishi Gas Chemical (Manufactured by Kanto Chemical Co., Ltd.) and 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were charged and reacted for 7 hours while refluxing at 100 ° C under atmospheric pressure. Thereafter, 180.0 g of ortho xylene (Wako Pure Chemical Industries, Ltd.) as a diluting solvent was added to the reaction solution, and after standing, the water phase was removed. Again, neutralization and washing were carried out, and ortho-xylene was distilled off under reduced pressure to obtain 35.2 g of a brown solid resin (IMR-1).

The obtained resin (IMR-1) had Mn: 1765, Mw: 3250, and Mw / Mn: 1.84. The carbon concentration was 79.8 mass% and the oxygen concentration was 8.5 mass%.

As a result of thermogravimetric analysis (TG), the 10% heat-reduction temperature of the obtained resin (IMR-1) was 350 ° C or more and less than 400 ° C. Thus, it was evaluated that it is possible to apply to a high-temperature bake.

As a result of evaluating the solubility in PGME and PGMEA, the resin (IMR-1) was evaluated to have excellent solubility at 10 wt% or more (evaluation A).

(Synthesis Example 7) Synthesis of Resin (IMR-2)

A four liter flask with an internal volume of 1 L, equipped with a Dimros cooling tube, a thermometer and a stirrer, was prepared. 26.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Company) and 50.9 g (280 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of IMX-2 obtained in Synthesis Example 2 were added to the four- , 100 mL of anisole (manufactured by Kanto Chemical Co., Ltd.) and 10 mL of oxalic acid dihydrate (manufactured by Kanto Chemical Co., Ltd.) were charged and reacted for 7 hours while refluxing at 100 ° C under normal pressure. Thereafter, 180.0 g of ortho xylene (Wako Pure Chemical Industries, Ltd.) as a diluting solvent was added to the reaction solution, and after standing, the water phase was removed. The organic phase solvent and the unreacted 4-biphenylaldehyde were distilled off under reduced pressure to obtain 37.1 g of a brown solid resin (IMR-2).

The obtained resin (IMR-2) had Mn: 1482, Mw: 2610, and Mw / Mn: 1.76. The carbon concentration was 81.2 mass% and the oxygen concentration was 7.5 mass%.

As a result of thermogravimetric analysis (TG), the 10% heat loss temperature of the obtained resin (IMR-2) was 350 ° C or more and less than 400 ° C. Thus, it was evaluated that it is possible to apply to a high-temperature bake.

As a result of evaluating the solubility in PGME and PGMEA, the resin (IMR-2) was evaluated to have excellent solubility at 10 wt% or more (evaluation A).

(Comparative Synthesis Example 1) Synthesis of comparative resin

A four-necked flask with an inner volume of 10 L was provided with a bottom-detachable flask equipped with a Dimros cooling tube, a thermometer and a stirrer. To this four-necked flask, 1.09 kg (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of 1,5-dimethylnaphthalene, 2.1 kg (40 mol% formaldehyde solution: 28 mol, manufactured by Mitsubishi Gas Chemical Co., ) And 0.97 mL of 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.), and the reaction was carried out for 7 hours while refluxing at 100 DEG C under normal pressure. Thereafter, 1.8 kg of ethylbenzene (a reagent grade manufactured by Wako Pure Chemical Industries, Ltd.) as a diluting solvent was added to the reaction solution, and after standing, the water phase of the bed was removed. Again, neutralization and washing were carried out, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of a dimethylnaphthalene formaldehyde resin having a pale brown solid.

The molecular weight of the obtained dimethylnaphthalene formaldehyde was Mn: 562, Mw: 1168, and Mw / Mn: 2.08. The carbon concentration was 84.2 mass% and the oxygen concentration was 8.3 mass%.

Subsequently, an inner volume 0.5 L four-necked flask equipped with a Dimros cooling tube, a thermometer and a stirring blade was prepared. 100 g (0.51 mol) of the dimethyl naphthalene formaldehyde resin obtained as described above and 0.05 g of paratoluenesulfonic acid were charged into the four-necked flask under nitrogen flow, and the mixture was heated to 190 DEG C and heated for 2 hours, Respectively. Thereafter, again 52.0 g (0.36 mol) of 1-naphthol was added, and further the temperature was raised to 220 ° C and the reaction was carried out for 2 hours. After solvent dilution, neutralization and washing were carried out, and the solvent was removed under reduced pressure to obtain 126.1 g of a modified resin (CR-1) as a dark brown solid.

The obtained resin (CR-1) had Mn of 885, Mw of 2220 and Mw / Mn of 4.17. The carbon concentration was 89.1 mass% and the oxygen concentration was 4.5 mass%.

(Examples 1 to 7 and Comparative Example 1)

A composition for forming a lower layer film for lithography was prepared so as to have the composition shown in Table 1 below. That is, the following materials were used.

Acid generator: di-tertiary butyl diphenyl iodonium nonafluoromethane sulfonate ("DTDPI" in Table 1) manufactured by Midori Kagaku Co.,

Crosslinking agent: NIKARAK MX270 (" NIKARAK " in Table 1) manufactured by Sanwa Chemical Co.,

Organic solvent: propylene glycol monomethyl ether (" PGME " in Table 1)

NOVOLAC: PSM4357 from Army Ei Chemical Corporation

Next, the lower layer film forming compositions of Examples 1 to 7 and Comparative Example 1 were spin-coated on a silicon substrate, and then baked at 240 캜 for 60 seconds and again at 400 캜 for 120 seconds to form a lower layer Respectively.

Then, an etching test was carried out under the following conditions to evaluate the etching resistance. The evaluation results are shown in Table 1.

[Etching test conditions]

Etching apparatus: RIE-10NR manufactured by Samco International

Output: 50W

Pressure: 20 Pa

Time: 2min

Etching gas

Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)

[Evaluation of etching resistance]

The evaluation of the etching resistance was carried out in the following order.

First, a novolak underlayer film was prepared under the same conditions as in Example 1, except that novolak (PSM4357, manufactured by Kuniei Chemical Co., Ltd.) was used instead of the compound (IMX-1) used in Example 1. The lower layer film of the novolak was subjected to the above-described etching test, and the etching rate at this time was measured.

Next, the lower layer films of Examples 1 to 7 and Comparative Example 1 were subjected to the same etching test, and the etching rate at that time was measured.

Then, with respect to the etching rate of the novolac underlayer film, the etching resistance was evaluated based on the following evaluation criteria.

 [Evaluation standard]

S: the etching rate is less than -30% as compared with the lower layer film of novolac

A: The etching rate was less than -10% as compared with the novolak underlayer film

B: an etching rate of -10% to + 5%, as compared with the lower layer film of novolak;

C: Etching rate exceeded + 5% as compared with the lower layer film of novolac

[Table 1]

(Example 8)

Subsequently, a composition for forming a lower layer film for lithography used in Example 1 was applied on a SiO ₂ substrate having a film thickness of 300 nm and baked at 240 캜 for 60 seconds and again at 400 캜 for 120 seconds to form a lower layer film having a film thickness of 60 nm Respectively. On this lower layer film, a resist solution for ArF was applied and baked at 130 캜 for 60 seconds to form a photoresist layer having a thickness of 120 nm.

On the other hand, as the ArF resist solution, 5 parts by mass of the compound of the following formula (11), 1 part by mass of triphenylsulfonium nonafluoromethane sulfonate, 2 parts by mass of tributylamine, and 92 parts by mass of PGME Were used.

The compound of formula (11) was prepared as follows. Namely, 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy- gamma -butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, 0.38 g of isobutyronitrile was dissolved in 80 mL of tetrahydrofuran to prepare a reaction solution. The reaction solution was polymerized for 22 hours while maintaining the reaction temperature at 63 캜 in a nitrogen atmosphere, and then the reaction solution was added dropwise to 400 mL of n-hexane. The resulting resin thus obtained was coagulated and purified, and the resulting white powder was filtered and dried overnight at 40 占 폚 under reduced pressure to obtain a compound represented by the following formula.

(35)

In the formula (11), "40", "40", and "20" attached to the parentheses indicate the proportion of each constituent unit and do not represent a block copolymer.

Subsequently, the photoresist layer was exposed using an electron beam imaging apparatus (ELO-7500, 50 keV, manufactured by Elionics), baked (PEB) at 115 캜 for 90 seconds, and 2.38% by mass of tetramethylammonium hydroxide (TMAH) And then developed with an aqueous solution for 60 seconds to obtain a positive resist pattern.

(Comparative Example 2)

A photoresist layer was formed directly on the SiO ₂ substrate in the same manner as in Example 8 except that the formation of the lower layer film was not performed, thereby obtaining a positive resist pattern.

[evaluation]

The shape of the obtained resist pattern of 40 nm L / S (1: 1) and 80 nm L / S (1: 1) was applied to each of Example 8 and Comparative Example 2 using an electron microscope (S-4800) manufactured by Hitachi, Respectively. Regarding the shape of the resist pattern after the development, evaluation was made with no pattern collapse, with good rectangularity as "good", and as "poor" with no rectangularity. As a result of the above observations, the minimum line width having good rectangularity without pattern collapse was defined as " resolution " Furthermore, the minimum amount of electron beam energy capable of imaging a good pattern shape was taken as an index of evaluation. The results are shown in Table 2.

[Table 2]

As is apparent from Table 2, the lower layer film of Example 8 was found to be significantly superior in both resolution and sensitivity as compared with Comparative Example 2. It was also confirmed that the shape of the resist pattern after development was good without any pattern collapse and rectangularity. Furthermore, from the viewpoint of the resist pattern shape after development, the lower layer film forming material for lithography of Example 1 showed good adhesion to the resist material.

(Example 9) Purification of IMX-1

300 g of a solution (5% by mass) obtained by dissolving the compound (IMX-1) obtained in Synthesis Example 1 in ethyl acetate in ethyl acetate was introduced into a four-neck flask (bottom detachable type) having a capacity of 1000 mL and heated to 80 캜 with stirring. Subsequently, 80 g of an oxalic acid aqueous solution (pH 1.3) was added, stirred for 5 minutes, and allowed to stand for 30 minutes. As it was separated into oil phase and water phase, the water phase was removed. After this operation was repeated once more, 80 g of ultrapure water was added to the obtained oil phase, stirred for 5 minutes, and then allowed to stand for 30 minutes to remove the water phase. This operation was repeated three times, and the pressure in the flask was reduced to 200 hPa or less while heating to 50 DEG C, whereby the residual water and ethyl acetate were concentrated and evaporated. Thereafter, heptane (made by Showa Denko Co.) of EL grade was added, and the IMX-1 having a reduced metal content was solidified by coagulation. The resulting white powder was filtered and dried overnight at 80 < 0 > C under reduced pressure to obtain the solvent-removed IMX-1.

(Reference example) Purification method by ion exchange resin

25 g of an ion exchange resin (Mitsubishi Chemical Dai Aon: SMT100-Mix resin) was swelled with cyclohexanone, filled into a Teflon (registered trademark) column, and 500 mL of PGME was passed through to replace the solvent. Subsequently, 500 g of a solution (10% by mass) in which IMX-1 obtained in Example 1 was dissolved in PGME was passed through to obtain a PGME solution of IMX-1.

Various metal contents of the 10% by mass PGME solution of IMX-1 before treatment and the solution obtained in Example 9 and Reference Example were measured by ICP-MS. The measurement results are shown in Table 3.

[Table 3]

The compound and the resin of the present embodiment have a high etching resistance to a fluorine-based gas and a relatively high solvent solubility, so that a wet process can be applied. Accordingly, the lower layer film forming material for lithography and the lower layer film using the compound or the resin of this embodiment can be widely and effectively used in various applications where these performances are required. Therefore, the present invention is applicable to, for example, electric insulating materials, resist resins, sealing resins for semiconductors, adhesives for printed wiring boards, electric laminated boards mounted on electric devices, Resin for resin for fiber reinforced plastic, resin for encapsulating liquid crystal display panel, coating material, coating agent, adhesive, coating material for semiconductor, resin for resist for semiconductor, lower layer of matrix resin, build-up laminate material, A resin for forming a film, and the like. Particularly, the present invention can be effectively used particularly in the fields of a lower layer film for lithography and a lower layer film for a multilayer resist.

The disclosure of Japanese Patent Application No. 2015-0145010 filed on July 22, 2015 is incorporated herein by reference in its entirety.

In addition, all documents, patent applications, and technical specifications described in the specification are incorporated herein by reference in their entirety to the same extent as if each individual document, patent application, do.

Claims (21)

A compound represented by the following formula (1).
[Chemical Formula 1]

(1), each X independently represents an oxygen atom, a sulfur atom or a non-substituted group; and each R ¹ independently represents a halogen group, a cyano group, a nitro group, an amino group, a hydroxyl group, a thiol group, , An alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, wherein the alkyl group, alkenyl group and aryl group , An ether bond, a ketone bond or an ester bond, and each R ² independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, Wherein at least one of R ² is a group containing a hydroxyl group or a thiol group and m is each independently an integer of 0 to 7 (where at least one of m is an integer of 1 to 7). ), p is independently 0 or 1, q is an integer of 0 to 2, n is 1 or 2.) The method according to claim 1,
Wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).
(2)

(In the formula (1-1), R ¹ , R ² , m, p, q and n are as defined in the formula (1).) 3. The method of claim 2,
Wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-2).
(3)

(2), each R ³ is independently an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, and R ¹ , p, q, , M ² is independently an integer of 0 to 5, m ³ is independently an integer of 1 to 6, m ² + m ³ is an integer of 1 to 6 It is an integer.) The method of claim 3,
Wherein the compound represented by the formula (1-2) is a compound represented by the following formula (1-3).
[Chemical Formula 4]

(In the formula (1-3), R ¹ , R ³ , p, q and n are the same as those described in the formula (1), and m ² is the same as that described in the formula (1-2).) 5. The method of claim 4,
Wherein the compound represented by the formula (1-3) is a compound represented by the following formula (1-4).
[Chemical Formula 5]

(In the formula (1-4), R ¹ and q are as defined in the formula (1).) 6. The method of claim 5,
The compound represented by the above formula (1-4) is a compound represented by the following formula (IMX-1).
[Chemical Formula 6]

A resin obtained by using the compound according to any one of claims 1 to 6 as a monomer. 8. The method of claim 7,
A resin obtained by reacting a compound according to any one of claims 1 to 6 with a compound having a crosslinking reactivity. 9. The method of claim 8,
Wherein the crosslinkable compound is at least one selected from aldehyde, ketone, carboxylic acid, carboxylic acid halide, halogen-containing compound, amino compound, imino compound, isocyanate and unsaturated hydrocarbon group-containing compound. A resin having a structure represented by the following formula (2).
(7)

(In the formula (2), each X independently represents an oxygen atom, a sulfur atom or a non-substituted group, and each R ¹ independently represents a halogen group, a cyano group, a nitro group, an amino group, a hydroxyl group, , An alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, wherein the alkyl group, alkenyl group and aryl group , An ether bond, a ketone bond or an ester bond, and each R ² independently represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a thiol group, Y is a single bond or an alkylene group having 1 to 20 carbon atoms, m is, independently of each other, an integer of 0 to 6 (provided that at least one of R ² is a group containing a hydroxyl group or a thiol group) Here, at least one of m is an integer of 1 to 6), p is Independently 0 or 1, q is an integer from 0 to 2, and n is 1 or 2.) A lower layer film forming material for lithography, which comprises the compound according to any one of claims 1 to 6 and / or the resin according to any one of claims 7 to 10. A composition for forming a lower layer film for lithography, which comprises the underlayer film forming material for lithography according to claim 11 and a solvent. 13. The method of claim 12,
A composition for forming a lower layer film for lithography, further comprising an acid generator. The method according to claim 12 or 13,
A composition for forming a lower layer film for lithography, further comprising a crosslinking agent. A lower layer film for lithography formed using the composition for forming a lower layer film for lithography as set forth in any one of claims 12 to 14. Forming a lower layer film on the substrate using the composition for forming a lower layer film as set forth in any one of claims 12 to 14, forming at least one photoresist layer on the lower layer film, Irradiating a predetermined region of the resist layer with radiation, and developing the resist pattern. A method of forming a lower layer film on a substrate by using the composition for forming a lower layer film as set forth in any one of claims 12 to 14 and forming a lower layer film on the lower layer film by using a resist interlayer film material containing silicon atoms Forming at least one photoresist layer on the intermediate layer film, irradiating a predetermined region of the photoresist layer with radiation, developing the resist pattern to form a resist pattern, The intermediate layer film is etched, the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained lower layer film pattern as an etching mask to form a pattern on the substrate. A process for producing an aqueous solution by contacting an acidic aqueous solution with a solution comprising the compound according to any one of claims 1 to 6 or the resin according to any one of claims 7 to 10 and an organic solvent which is not optionally miscible with water, Or a mixture thereof. 19. The method of claim 18,
Wherein the acidic aqueous solution comprises at least one inorganic acid aqueous solution selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or an aqueous solution of at least one inorganic acid selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, Sulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. 20. The method according to claim 18 or 19,
Wherein the organic solvent which is not optionally miscible with the water is selected from the group consisting of toluene, 2-heptanone, cyclohexanone, cyclopentanone, methylisobutylketone, propylene glycol monomethyl ether acetate, 1,2-diethoxy ketone, Ethyl acetate. 21. The method according to any one of claims 18 to 20,
Subjecting the solution to an extraction treatment with an acidic aqueous solution, and then subjecting the extract to further extraction with water.